JP2012508303A - Isocyanate trimerization catalyst system, precursor formulation, isocyanate trimerization process, rigid polyisocyanurate / polyurethane foam made therefrom, and process for making the foam - Google Patents

Abstract

The present invention provides isocyanate trimerization catalyst systems, precursor formulations, methods for trimerizing isocyanates, rigid foams made therefrom, and methods for making the foams. The trimerization catalyst system comprises (a) an imidazolium or imidazolinium cation; and (b) an isocyanate trimer derived anion and has a trimerization activation temperature in the range of 73 ° C. or less. The precursor formulation comprises (1) at least 25 weight percent polyol, (2) (a) an imidazolium or imidazolinium cation; and (c) an isocyanate trimer derived anion, based on the weight of the precursor formulation. Including less than 15% by weight trimerization catalyst system, based on the weight of the precursor formulation, having a trimerization activation temperature in the range of 73 ° C.

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application was filed on Nov. 10, 2008, “Isocyanate Trimerization Catalyst System, Precursor Formulation, Isocyanate Trimerization Method, Rigid Polyisocyanurate / Polyurethane Foam Made therefrom, And US Patent No. 61 / 113,196, entitled "Preparation of the Foam", the teaching of which is hereby incorporated by reference herein in its entirety. Which is incorporated herein by reference.

  The present invention relates to isocyanate trimerization catalyst systems, precursor formulations, methods for trimerizing isocyanates, rigid polyisocyanurate / polyurethane foams made therefrom, and methods for making the foams.

  Rigid polyisocyanurate / polyurethane (PIR) foams are widely known and used in many industries. PIR foams have both groups, namely urethane groups (obtained from the reaction of isocyanate —NCO groups and polyol hydroxyl groups) and excess —NCO groups relative to hydroxyl groups (isocyanate index greater than 100, eg 180-600) and isocyanurate rings derived from trimerization. Trimerization of -NCO groups is typically catalyzed by special catalysts such as tris (dimethylaminomethyl) phenol, potassium acetate and other catalysts. The highly crosslinked structure of the PIR foam is derived from the isocyanurate ring formed by trimerization of excess —NCO groups.

  PIR foams are always subject to stricter regulations regarding flame retardancy and low smoke generation. Flame retardant properties and low smoke emission are typically improved by the presence of an isocyanurate ring. However, current trimerization catalyst systems for producing such isocyanurate rings tend to be active only at high temperatures, which is typical in the central region of PIR foams. Thus, current trimerization catalyst systems tend to promote the formation of isocyanurate rings primarily in the central region of PIR foams. Although the use of current trimerization catalyst systems improves the flame retardant and fuming properties of the central region of PIR foam, there is a need to further improve such properties within the outer region of such PIR foam Is still there. The present invention promotes the formation of isocyanurate rings within the outer region of such PIR foam, and as a result, promotes improved flame retardant and fuming properties of the outer region of the PIR foam. The present invention promotes and increases the trimerization of isocyanurate rings in the outer region of the PIR foam by requiring a decrease in activation temperature. The present invention can further improve the adhesive properties, i.e. the tensile bond strength of the double steel facer of the PIR foam panel, for example in a lamination process.

  The present invention provides isocyanate trimerization catalyst systems, precursor formulations, methods for trimerizing isocyanates, PIR foams made therefrom, and methods for making the foams.

  In one embodiment, the present invention provides a trimerization catalyst system comprising (a) an imidazolium or imidazolinium cation; and (b) an isocyanate trimer derived anion and having a trimerization activation temperature in the range of 73 ° C. or less. I will provide a.

  In an alternative embodiment, the present invention provides (1) at least 25% by weight of polyol, based on the weight of the precursor formulation; (2) (a) an imidazolium or imidazolinium cation; and (c) an isocyanate trimer. Less than 15% by weight of trimerization catalyst system, based on the weight of the precursor formulation, containing a derived anion and having a trimerization activation temperature in the range of 73 ° C. or less; and (3) one or Multiple surfactants, one or more flame retardants, water, one or more antioxidants, one or more foaming aids, one or more urethane catalysts, one or more trimerization aids Further provided is a precursor formulation comprising a catalyst (other than the trimerization catalyst system described herein), or a combination thereof.

  In an alternative embodiment, the present invention provides (1) one or more monomers selected from the group consisting of isocyanates, diisocyanates, triisocyanates, isocyanate oligomers, salts of any of them, and mixtures of any of them. Providing a trimerization catalyst system comprising (2) (a) an imidazolium or imidazolinium cation; and (b) an isocyanate trimer derived anion and having a trimerization activation temperature in the range of 73 ° C. or less. (3) trimerizing one or more monomers in the presence of a trimerization catalyst; and (4) the step of producing an isocyanurate trimer thereby producing a trimerization of isocyanate. A method is further provided.

  In an alternative embodiment, the present invention provides (1) one or more monomers selected from the group consisting of isocyanates, diisocyanates, triisocyanates, isocyanate oligomers, salts of any of them, and mixtures of any of them. (2) providing a polyol; (3) (a) an imidazolium or imidazolinium cation; and (b) a trimerization activation in the range of 73 ° C. or less, comprising an isocyanate trimer derived anion. Providing a trimerization catalyst system having a temperature; (4) optionally one or more surfactants, one or more flame retardants, water, one or more antioxidants, one Or a plurality of blowing aids, one or more urethane catalysts, one or more trimerization cocatalysts, or Providing a combination; (5) contacting one or more monomers and a polyol, optionally with one or more surfactants, and optionally with one or more flame retardants; And, optionally, water, and optionally one or more antioxidants, and optionally one or more blowing aids in the presence of a trimerization catalyst system, and optionally Contacting the one or more urethane catalysts, and optionally one or more trimerization cocatalysts; (6) for making a PIR foam comprising the step of thereby generating a PIR foam A method is further provided.

  In an alternative embodiment, the present invention is a trimerization catalyst system comprising an imidazolium or imidazolinium cation and an isocyanate trimer derived anion, optionally with one or more surfactants, optionally One or more flame retardants, optionally water, optionally one or more antioxidants, optionally one or more foaming aids, optionally one or more Presence of a trimerization catalyst system comprising a further trimerization temperature in the range of 73 ° C. or less, comprising an additional urethane catalyst, and optionally one or more trimerization cocatalysts, or optionally combinations thereof From isocyanates, diisocyanates, triisocyanates, isocyanate oligomers, salts of any of them and mixtures of any of them Comprises the reaction product of one or more monomers and a polyol selected from the group, further provides a PIR foam.

In an alternative embodiment, the present invention is a trimerization catalyst system comprising an imidazolium or imidazolinium cation and an isocyanate trimer derived anion, optionally with one or more surfactants, optionally One or more flame retardants, optionally water, optionally one or more antioxidants, optionally one or more foaming aids, optionally one or more Isocyanates, diisocyanates, triisocyanates, isocyanate oligomers, in the presence of a trimerization catalyst system comprising a further polyurethane catalyst and optionally one or more trimerization cocatalysts, or optionally combinations thereof One or more of the compounds selected from the group consisting of salts of any of the above and mixtures of any of them A PIR foam comprising the reaction product of a chromatography with a polyol polyisocyanurate trimerization ratio as measured by ATR-FTIR spectroscopy at a depth 12mm from the upper surface of the rigid foam _(Abs 1410 _/ Abs ₁₅₉₅ Further provided is a PIR foam wherein) is at least 5.

  In an alternative embodiment, the invention provides that the imidazolium cation has the structure

Wherein E is a C ₂ or C ₆ unsaturated bond, X is selected from the group consisting of H, C ₁ -C ₁₈ , P, Si, N, and any combination thereof, R ₁ is H, C ₁ -C ₁₈ , Si and any combination thereof are selected, and R ₂ is selected from the group consisting of H, C ₁ -C ₁₈ , Si and any combination thereof)
In accordance with any of the above embodiments except for having an isocyanate trimerization catalyst, a precursor formulation, a method for trimerizing isocyanate, a PIR foam made therefrom, and a method for making the foam Provide a method.

  In an alternative embodiment, the invention provides that the imidazolinium cation has the structure

Wherein E is a saturated hydrocarbon bond, X is selected from the group consisting of H, C ₁ -C ₁₈ , P, Si, N and any combination thereof, R ₁ is H, C ₁ -C ₁₈ , Si and any combination thereof, and R ₂ is selected from the group consisting of H, C ₁ -C ₁₈ , Si and any combination thereof)
Except for having an isocyanate trimerization catalyst, a precursor formulation, a method for trimerizing isocyanate, a PIR foam made therefrom, and a method for making the foam Provide a method.

In an alternative embodiment, the present invention, (X is selected from _H, C 1 _{-C 18} and the group consisting of any combination thereof, _{R 1} is _H, a C 1 _{-C 18} and any combination thereof Isocyanate trimerization catalyst, precursor formulation according to any of the above embodiments (except that R ₂ is selected from the group consisting of H, C ₁ -C ₁₈ and any combination thereof) Provided are methods for trimerizing isocyanates, PIR foams made therefrom, and methods for making the foams.

In an alternative embodiment, the present invention is according to any of the above embodiments (except that X is selected from the group consisting of H, R ₁ is tert-butyl and R ₂ is tert-butyl). Provided are an isocyanate trimerization catalyst, a precursor formulation, a method for trimerizing isocyanate, a PIR foam made therefrom, and a method for making the foam.

  In an alternative embodiment, the invention provides that the isocyanate trimer derived anion is selected from the group consisting of carboxylate, carbonate, phenoxide, amide, amidinate, imide, phosphide, thiocyanate, thioisocyanate, isocyanate, cyanate and fluoride. Provided is an isocyanate trimerization catalyst, a precursor formulation, a method for trimerizing isocyanate, a PIR foam made therefrom, and a method for making the foam, according to any of the above embodiments To do.

  In an alternative embodiment, the present invention provides an isocyanate trimerization catalyst according to any of the above embodiments (except that the isocyanate trimer derived anion is selected from the group consisting of carboxylate, carbonate, phenoxide and fluoride), Provided are precursor formulations, methods for trimerizing isocyanate, PIR foams made therefrom, and methods for making the foams.

  In an alternative embodiment, the present invention provides an isocyanate trimerization catalyst, precursor formulation, for trimerizing isocyanates according to any of the above embodiments, except that the isocyanate trimer derived anion is a carboxylate. Methods, PIR foams made therefrom, and methods for making the foams are provided.

  In an alternative embodiment, the invention provides that the carboxylate has the structure

Wherein X ′ is selected from the group consisting of H, C ₁ -C ₁₈ , aliphatic, aromatic, cyclic, acyclic, acyl, and derivatives thereof.
Except for having an isocyanate trimerization catalyst, a precursor formulation, a method for trimerizing isocyanate, a PIR foam made therefrom, and a method for making the foam Provide a method.

  In an alternative embodiment, the present invention provides the above (except that the carboxylate is selected from the group consisting of formate, acetate, octanoate, 2-ethylhexanoate, benzoate, and substituted derivatives thereof). Provided are an isocyanate trimerization catalyst, a precursor formulation, a method for trimerizing isocyanate, a PIR foam made therefrom, and a method for making the foam according to any embodiment.

  In an alternative embodiment, the present invention provides an isocyanate trimerization catalyst, precursor formulation, method for trimerizing isocyanate according to any of the above embodiments except that the isocyanate trimer derived anion is acetate. , PIR foams made therefrom, and methods for making the foams.

  In an alternative embodiment, the present invention provides a process wherein the trimerization catalyst system is 1,3-di-tert-butylimidazolidinium acetate or 1,3-di-tert-butyl-2,3-dihydro-1H-imidazolium. Isocyanate trimerization catalyst, precursor formulation, method for trimerizing isocyanate, foam made therefrom, and to make the foam, according to any embodiment above (with the exception of acetate) Provide a way.

  In an alternative embodiment, the present invention provides a PIR foam according to any of the above embodiments, except that the foam is used as a thermal insulation material, such as a thermal insulation foam for construction or a thermal insulation foam for electrical products, and the A method for making a foam is provided.

  For the purpose of illustrating the invention, there are shown in the drawings exemplary forms, but it is to be understood that the invention is not limited to the precise arrangements and instrumentalities shown.

2 is an exemplary graph showing the trimer content of one exemplary inventive foam and a comparative foam.

  The present invention provides isocyanate trimerization catalyst systems, precursor formulations, methods for trimerizing isocyanates, PIR foams made therefrom, and methods for making the foams.

  The isocyanate trimerization catalyst system comprises (a) an imidazolium or imidazolinium cation; and (b) an isocyanate trimer derived anion. The isocyanate trimerization catalyst system has a trimerization activation temperature in the range of 73 ° C. or less. All individual values and subranges from below 73 ° C. are included herein and disclosed herein. For example, the activation temperature may be from a lower limit of 25, 35, 45, or 55 ° C to an upper limit of 45, 55, 65, 70, or 73 ° C. For example, the isocyanate trimerization catalyst system has a trimerization activation temperature in the range of 70 ° C or lower, or 68 ° C or lower, or 66 ° C or lower, or 65 ° C or lower. In one embodiment, the isocyanate trimerization catalyst system does not have any polymer support.

  The imidazolium cation component of the isocyanate trimerization catalyst system has the following structure:

Wherein E is a C ₂ or C ₆ unsaturated bond, X is selected from the group consisting of H, C ₁ -C ₁₈ , P, SiN and any combination thereof, R ₁ is H, C ₁ ˜C ₁₈ , Si and any combination thereof, and R ₂ is selected from the group consisting of H, C _{1 to} C ₁₈ , Si and any combination thereof)
Have

  The imidazolinium cation component of the isocyanate trimerization catalyst system has the following structure:

Wherein E is a saturated hydrocarbon bond, X is selected from the group consisting of H, C ₁ -C ₁₈ , P, Si, N and any combination thereof, R ₁ is H, C ₁ -C ₁₈ , Si and any combination thereof, and R ₂ is selected from the group consisting of H, C ₁ -C ₁₈ , Si and any combination thereof)
Have

In one embodiment, X is selected from _H, C 1 _{-C 18} and the group consisting of any combination thereof, _{R 1} is selected from _H, C 1 _{-C 18} and the group consisting of any combination thereof , R ₂ is selected from the group consisting of H, C ₁ -C ₁₈ and any combination thereof. In one embodiment, X is selected from the group consisting of H, R ₁ is tert-butyl and R ₂ is tert-butyl.

  As used herein, an isocyanate trimer derived anion refers to an anion that promotes the trimerization of isocyanate in the presence of one or more imidazolium or imidazolinium cations. The isocyanate trimer derived anion is an anion selected from the group consisting of, for example, carboxylate, carbonate, phenoxide, amide, amidinate, imide, phosphide, thiocyanate, thioisocyanate, isocyanate, cyanate, and fluoride. In the alternative, the isocyanate trimer derived anion is selected from the group consisting of carboxylate, carbonate, phenoxide, and fluoride. In another alternative, the isocyanate trimer derived anion is a carboxylate. Carboxylate has, for example, the following structure

Wherein X ′ is selected from the group consisting of H, C ₁ -C ₁₈ , aliphatic, aromatic, cyclic, acyclic, acyl, and derivatives thereof.
You may have. The carboxylate may be selected, for example, from the group consisting of formate, acetate, octanoate, 2-ethylhexanoate, benzoate, and substituted derivatives thereof. In the alternative, the isocyanate trimer derived anion is acetate.

  In one embodiment, the trimerization catalyst system is 1,3-di-tert-butylimidazolidinium acetate or 1,3-di-tert-butyl-2,3-dihydro-1H-imidazolium acetate.

  The precursor formulation according to the present invention comprises (a) one or more polyols; (b) the trimerization catalyst system of the present invention as described herein above; and (c) one or more interfaces as required. Activator, one or more flame retardants, water, one or more antioxidants, one or more foaming aids, one or more urethane catalysts, one or more trimerization cocatalysts, or Including combinations thereof. The precursor formulation includes at least 25% by weight of one or more polyols as described herein below, based on the weight of the precursor formulation. All individual values and subranges from at least 25% by weight are included herein and disclosed herein. For example, the weight percent of one or more polyols is from 45, 50, 55, 65, 75, 85, 90, 95, or 98 W% from the lower limit of 25, 30, 35, 40, or 45 wt% (W%). It may be up to the upper limit. For example, the precursor formulation includes 25-98, or 30-98, or 35-98, or 45-95% by weight of one or more polyols based on the weight of the precursor formulation. The precursor formulation includes up to 15% by weight of the trimerization catalyst system of the present invention as described hereinabove, based on the weight of the precursor formulation. All individual values and subranges from 15 wt% or less are included herein and disclosed herein. For example, the weight percent of the trimerization catalyst system may be from a lower limit of 0.1, 1, 2, 4, 5, 7, or 10 W% to an upper limit of 10, 12, 14, or 15 W%. For example, the precursor formulation includes 2-15, or 4-15, or 5-15 or 7-15, or 10-15% by weight of the trimerization catalyst system of the present invention, based on the weight of the precursor formulation. .

  The trimerization catalyst system of the present invention trimerizes one or more monomers selected from the group consisting of, for example, isocyanates, diisocyanates, triisocyanates, isocyanate oligomers, salts of any of them, and mixtures of any of them. Can be used to form one or more isocyanurate rings.

  In addition, PIR foams can be formed using the trimerization catalyst system of the present invention. The methods for forming PIR foams described in more detail herein below generally include the following: (1) isocyanates, diisocyanates, triisocyanates, isocyanate oligomers, salts of any of them, and any of them Providing one or more monomers selected from the group consisting of a mixture of: (2) providing a polyol; (3) (a) an imidazolium or imidazolinium cation; and (b) an isocyanate trimer Providing a trimerization catalyst system comprising a body-derived anion and having a trimerization activation temperature in the range of 73 ° C. or less; and (4) optionally one or more surfactants, one or more Flame retardant, water, one or more antioxidants, one or more foaming aids, one or more Providing a urethane catalyst, one or more trimerization cocatalysts, or a combination thereof; (5) contacting one or more monomers and a polyol, optionally one or Of a plurality of surfactants, and optionally one or more flame retardants, and optionally water, and optionally one or more antioxidants, and optionally a trimerization catalyst system Contacting one or more foaming aids in the presence, and optionally one or more urethane catalysts, and optionally one or more trimerization cocatalysts; and (6) it To produce a polyisocyanurate / polyurethane rigid foam.

  The PIR foams according to the present invention can preferably be produced by using the above-mentioned trimerization catalyst system in combination with a conventional urethane catalyst in a urethane formulation.

  As used herein, the term “isocyanate” refers to any compound comprising a polymer comprising at least one isocyanate group, such as monoisocyanates and organic polyisocyanates. Representative organic polyisocyanates that are suitably used include, but are not limited to, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate. Aromatic diisocyanates such as crude toluene diisocyanate, methylene diphenyl diisocyanate, and crude methylene diphenyl diisocyanate; aromatic triisocyanates such as tris- (4-isocyanatophenyl) methane and 2,4,6-toluentose (isocyanate); Aromatic tetra (isocyanate) such as 4′-dimethyldiphenylmethane-2,2 ′, 5 ′, 5′-tetra (isocyanate); alkylaryl polyisocyanate such as xylene diisocyanate; hexa Styrene-1,6-diisocyanate, ethylene diisocyanate, aliphatic polyisocyanates such as dicyclohexylmethane and 4,4'-diisocyanate, and mixtures thereof. Other organic polyisocyanates include polymethylene polyphenyl isocyanate, hydrogenated methylene diphenyl isocyanate, m-phenylene diisocyanate, naphthylene-1,5-diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4 ′. -Biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, isophorone Diisocyanate, 1,3-bis- (isocyanatomethyl) benzene, cumene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate Socyanate, 4-bromo-1,3-phenylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 2,4′-diisocyanate diphenyl ether, 5,6-dimethyl-1,3-phenylene diisocyanate, 2,4 -Dimethyl-1,3-phenylene diisocyanate, 4,4-diisocyanate diphenyl ether, benzidine diisocyanate, 4,6-dimethyl-1,3-phenylene diisocyanate, 9,10-anthracene diisocyanate, 4,4'-diisocyanate Dibenzyl, 3,3′-dimethyl-4,4′-diisocyanate diphenylmethane, 2,6′-dimethyl-4,4′-diisocyanate diphenyl, and mixtures thereof. Higher functionality polyisocyanates such as dimers and in particular NCO-terminated oligomers of isocyanates containing isocyanate rings and prepolymers and mixtures of the aforementioned isocyanates are also suitable. Such isocyanates, prepared by reacting excess isocyanate with active hydrogen compounds such as polyols, sometimes referred to as pseudo-prepolymers, preferably at least 2 moles of isocyanate groups and 1 mole of activity Those prepared by reacting with a hydrogen-containing compound are also suitable. These polyisocyanates are prepared by conventional methods known in the art, such as phosgenation of the corresponding organic amine.

  In one embodiment, aromatic polyisocyanates for the production of PIR foams include, but are not limited to, its 2,4′-isomer, 2,2′-isomer, and 4,4′- Mention may be made of mixtures of diphenylmethane diisocyanate (MDI) in the form of isomers and mixtures thereof and / or MDI oligomers known as MDI polymers. In the alternative, the polyisocyanate may be a so-called MDI polymer product. These are mixtures of polymethylene polyphenylene polyisocyanates in MDI monomers.

  In one embodiment, when making a PIR foam, the amount of monoisocyanate is generally less than 10% by weight of total isocyanate, less than 7% by weight of total isocyanate, less than 5% by weight of total isocyanate, and 2% by weight of total isocyanate. Less than or none.

In the practice of the present invention, active hydrogen compounds that are suitably reacted with isocyanates include any compound that includes a polymer that includes at least one active hydrogen moiety. For the purposes of the present invention, an active hydrogen moiety is a hydrogen atom that exhibits significant activity by the Zerewitnoff test described by Kohler in Journal of American Chemical Society, 49, 3181 (1927) because of its position in the molecule. Refers to the part containing Examples of such active hydrogen moieties are _{-COOH, -OH, -NH 2, -CONH} 2, -SH, and -CONH-. Hereinafter, such compounds will be referred to as monools (one active hydrogen moiety per molecule) and polyols (two or more active hydrogen moieties per molecule). The number average functionality of the polyol (s) or polyol blend suitable for producing the PIR foams of the present invention is in the range of 2-8, alternatively in the range of 3-8, and the hydroxyl equivalent weight is 60-560. In the alternative, it is in the range of 90-400.

  Typical active hydrogen compounds include monools and polyols, amines including polyamines, amides including polyamides, mercaptans including polymercaptans, acids including polyacids, and the like. Examples of suitable hydroxyl compounds are as follows (including mixtures thereof): monohydric alcohols such as ethanol, propanol and butanol and monohydric phenols such as phenol. Of particular interest are polyols such as polyether polyols, polyester polyols, homopolymers and copolymers of hydroxyalkyl acrylates and methacrylates, polyepoxide resins, phenol-formaldehyde resins, polyhydroxy-terminated polyurethane polymers, polyhydroxyl-containing phosphorus compounds and polyvalent thioethers. Alkylene oxide adducts, acetals including polyacetals, aliphatic and aromatic polyols and thiols (including polythioethers), ammonium and amines including polyamines, amines including aliphatic and heterocyclic amines, and mixtures thereof . Also used are alkylene oxide adducts of compounds containing two or more different groups included in the types defined above, such as amino alcohols containing amino and hydroxyl groups. Alkylene adducts of compounds containing one —SH group and one —OH group and compounds containing amino groups and —SH groups are also used. Examples of polyether polyols used as polyols in the practice of the present invention include polyalkylene polyether polyols such as diols such as ethylene glycol, propylene glycol, butylene glycol, and diethylene glycol. Examples of alcohols that are advantageously used as initiators in the production of polyether polyols include, but are not limited to, methanol, ethanol, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4- Butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,7-heptanediol, glycerol, 1,1,1-trimethylolpropane, 1,1,1-tri Examples include methylolethane, hexane-1,2,6-triol, α-methylglucoside, pentaerythritol, and sorbitol. Among the terms “alcohol” are compounds derived from phenols such as 2,2- (4,4′-hydroxyphenyl) propane, commonly known as bisphenol A; sugars such as sucrose, glucose, fructose, etc. included. Examples of alkylene oxides advantageously used in the preparation of polyether polyols include ethylene oxide, propylene oxide, butylene oxide, amylene oxide and two or more random or block copolymers of these oxides; glycidol; methyl glycidyl ether, t- Examples include glycidyl ethers or thioethers such as butyl glycidyl ether and phenyl glycidyl ether. The polyester polyol is a reaction product of a polycarboxylic acid and an alcohol, particularly a polyhydric alcohol. Examples of suitable polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, tapsinic acid, maleic acid, fumaric acid, glutaconic Acids, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α, β-diethylsuccinic acid, isophthalic acid, terephthalic acid, hemimellitic acid and 1,4-cyclohexane-dicarboxylic acid. . Any suitable alcohol is used, including both aliphatic and aromatic. Examples of suitable alcohols are the polyhydric alcohols previously described herein. The term “polyhydric alcohol” also includes compounds derived from phenols such as 2,2- (4,4′-hydroxyphenyl) propane, commonly known as bisphenol A; polyacetone polyols and the like.

  Other polyols suitably used include, but are not limited to, polyalkylene polyamines such as ethylene diamine; amino alcohols such as amino ethanol; esters of phosphoric acid, sulfonic acid and boric acid; cellulose-like polymers such as starch and methyl cellulose; Peptides and polypeptides; methylol resins such as urea-formaldehyde and melamine formaldehyde; lactones (such as ε-caprolactone or a mixture of ε-caprolactone and alkylene oxide) and polyfunctional initiators (such as polyhydric alcohols, amines or amino alcohols); Lactone polyols prepared by reacting are mentioned. In one embodiment, the polyalkylene ether diol may be an ethylene glycol, diethylene glycol, triethylene glycol, ethoxylated glycerin, ethylene oxide and / or propylene oxide polyether diol. The specific isocyanate and active hydrogen compounds and their amounts used in the practice of the present invention will depend on the specific end use application desired. Such a selection is within the skill of the art for such end use.

  In addition to the isocyanates, active hydrogens, and trimerization catalyst systems already described, other components such as surfactants and blowing agents are often advantageously included.

  In addition to the above-described components of the FIR foam formulation, other materials such as surfactants, foaming agents, fillers, dyes, pigments, crosslinking agents, chain extenders, flame retardants and anti-smoke agents may be used. .

  The trimerization catalyst system according to the present invention is useful for the formation of foam products for hard and flame retardant applications where usually a high isocyanate index is required. In this specification, the isocyanate index is the theoretically required stoichiometric amount of polyisocyanate required to react with all active hydrogen in the reaction mixture, divided by the actual amount of polyisocyanate used, multiplied by 100 Indicates the value. For purposes of the present invention, the isocyanate index is represented by the formula: isocyanate index = (Eq NCO / Eq of active hydrogen) × 100. In the formula, Eq NCO is the number of NCO functional groups in the polyisocyanate, and Eq of active hydrogen is the number of equivalent active hydrogen atoms.

  Foam products made with an isocyanate index of 80-800 are within the scope of the present invention. According to another aspect of the invention, the isocyanate index is 100-700, 150-650, 150-600, or 180-500.

  Foaming agents include, but are not limited to, isobutene, dimethyl ether, water, methylene chloride, acetone, chlorofluorocarbon (CFC), hydrofluorocarbon (HFC), hydrochlorofluorocarbon (HCFC), and hydrocarbons. Non-limiting examples of HFCs include HFC-245fa, HFC-134a, HFC-152a, HFC-227ea, and HFC-365. Illustrative examples of HCFC include HCFC-141b, HCFC-22, and HCFC-123. Examples of hydrocarbons include n-pentane, isopentane, cyclopentane, etc., or any combination thereof. The amount of blowing agent used may vary based on, for example, the intended use and application of the foam product and the desired foam stiffness and density. In the foam formulation and method for preparing the PIR foams of the present invention, the blowing agent is 1 to 80 parts by weight (pphp), 5 to 60 pphp, 7 to 60 pphp, 10 to 60 pphp, 12 to 100 parts by weight of polyol. It is present in an amount of 60 pphp, 14-40 pphp, or 16-25 pphp. If water is present in the formulation as a blowing agent or in other applications, the water is present in an amount up to about 15 pphp. In other words, water can range from 0 to 15 pphp. In other embodiments, the water can range from 0-10 pphp, 0.1-10 pphp, 0-8 pphp, 0-6 pphp, 0.3-5 pphp, or 0.4-4 pphp.

  In the process of making the PIR foam, the urethane catalyst accelerates the reaction to produce polyurethane. Urethane catalysts suitable for use herein include, but are not limited to, metal salt catalysts such as organotin, as well as triethylenediamine (TEDA), N-methylimidazole, 1,2-dimethylimidazole, N-methylmorpholine. , N-ethylmorpholine, triethylamine, N, N′-dimethylpiperazine, 1,3,5-tris (dimethylaminopropyl) hexahydrotriazine, 2,4,6-tris (dimethylaminomethyl) phenol, N-methyldicyclohexyl Amine, pentamethyldipropylenetriamine, N-methyl-N ′-(2-dimethylamino) -ethyl-piperazine, tributylamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine, di Tylaminocyclohexylamine, pentamethyldipropylene-triamine, triethanolamine, dimethylethanolamine, bis (dimethylaminoethyl) ether, tris (3-dimethylamino) propylamine, 1,8-diazabicyclo [5.4.0] Examples include amine compounds such as undecene (DBU), or acid block derivatives thereof, and any mixtures thereof.

  To prepare the PIR foams of the present invention, the urethane catalyst can be present in the formulation from 0-15 pphp, 0-10 pphp, 0-8 pphp, 0-6 pphp, 0-4 pphp, 0-2 pphp, or 0-1 pphp. In another embodiment, the urethane catalyst is present from 0 to 0.8 pphp, 0 to 0.6 pphp, 0 to 0.4 pphp, or 0 to 0.2 pphp.

  To prepare the PIR foams of the present invention, any trimerization co-catalyst is included in the formulation at 0-15 pphp, 0-10 pphp, 0-8 pphp, 0-6 pphp, 0-4 pphp, 0-2 pphp, or 0 There can be 1 pphp. In another embodiment, the urethane catalyst is present from 0 to 0.8 pphp, 0 to 0.6 pphp, 0 to 0.4 pphp, or 0 to 0.2 pphp.

  Various additives can be used in the PIR foam formulation to tailor specific properties during the manufacture of the foam or as needed for end use of the foam product. Additives include, but are not limited to, pore stabilizers, flame retardants, chain extenders, epoxy resins, acrylic resins, fillers, pigments, or any combination thereof. It will be appreciated that other mixtures or materials known in the art can be included in the foam formulation and are within the scope of the present invention.

  Examples of the pore stabilizer include surfactants such as organic polysiloxane. Surfactants are 0.5-10 pphp, 0.6-9 pphp, 0.7-8 pphp, 0.8-7 pphp, 0.9-6 pphp, 1-5 pphp, or 1.1-1.1 in the PIR foam formulation. It can be present in an amount of 4 pphp. Useful flame retardants include halogenated organophosphorus compounds and non-halogenated compounds. For example, trichloropropyl phosphate (TCPP) is a halogenated flame retardant and triethyl phosphate ester (TEP) is a non-halogenated flame retardant. Depending on the end-use foam utilization, the flame retardant may be present in the foam formulation in an amount of 0-50 pphp, 0-40 pphp, 0-30 pphp, or 0-20 pphp. In another embodiment, the flame retardant is present at 0-15 pphp, 0-10 pphp, 0-7 pphp, or 0-5 pphp. Chain extenders such as ethylene glycol and butanediol can also be used in the present invention.

  The present invention further provides a method for preparing a PIR foam comprising contacting at least one polyisocyanate with at least one active hydrogen-containing compound in the presence of an effective amount of the trimerization catalyst system of the present invention. To do.

  The trimerization catalyst system should be present in the foam formulation in an effective amount as a catalyst. In the PIR foam formulations of the present invention, the trimerization catalyst system comprises 0.05 to 15 parts by weight per 100 parts by weight of at least one active hydrogen-containing compound, including the weight contribution of a catalyst system diluent, such as diethylene glycol. Present in the amount of. In another embodiment, the trimerization catalyst system is in an amount of 0.4 to 10 parts by weight, or 0.4 to 9 parts by weight, or 0.8 to 8 parts by weight per 100 parts by weight of the at least one active hydrogen-containing compound. Exists. When the at least one active hydrogen-containing compound is at least one polyol, the trimerization catalyst system is present at 0.05 to 15 parts by weight (pphp) per 100 parts by weight polyol. In another embodiment, the catalyst composition is present in an amount of 0.2-10 pphp, 0.2-9.5 pphp, 0.4-9 pphp, 0.6-8.5 pphp, or 0.8-8 pphp.

  Given the number of components included in a PIR formulation, there are many different sequences in which the components are contacted or combined, and one skilled in the art can vary the order of addition of the components within the scope of the present invention. You will understand that Further, the method of producing the PIR foam comprises at least one pore stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, It may further comprise the presence of at least one additive selected from at least one pigment, or any combination thereof.

  In a further aspect of the invention, a premix of components other than at least one polyisocyanate can be first contacted and then at least one polyisocyanate can be added. For example, at least one active hydrogen-containing compound, at least one blowing agent, and the trimerization catalyst system of the present invention are first contacted to form a premix. The premix is then contacted with at least one polyisocyanate to produce a PIR foam by the method of the present invention. In a still further aspect of the invention, the same method can be used in which the premix further comprises at least one urethane catalyst. Similarly, the premix includes at least one pore stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, Or it may further contain at least one additive selected from any combination thereof.

  One embodiment of the present invention comprises (a) (i) at least one active hydrogen-containing polyol; (ii) 10 to 80 parts by weight (pphp) of blowing agent per 100 parts by weight of polyol; (iii) 0.5 to 10 pphp (Iv) 0-10 pphp water; (v) 0-50 pphp flame retardant; (vi) 0-10 pphp urethane catalyst; and (vii) 0.05-15 pphp of the trimerization catalyst of the present invention. Forming a premix comprising the system; and (b) contacting the premix with at least one polyisocyanate at an isocyanate index of 80-800.

  In one embodiment, the PIR foam of the present invention can be used as a thermal insulation material such as a thermal insulation foam for construction or a thermal insulation foam for electrical products.

  In another embodiment, the above ingredients necessary to make a PIR foam are sprayed together and mixed at the outlet from the spray nozzle to form an insulating foam on the wall.

  The following examples illustrate the invention but are not intended to limit the scope of the invention.

Preparation of trimerization catalyst system 1-ethyl, 2-methylimidazolium acetate, TCS 1 of the present invention
A 1.0 M solution of 1-ethyl, 2-methylimidazolium Cl was prepared in anhydrous MeOH. To this was added 1.05 equivalents of KOAc as a solid. The mixture was allowed to stir overnight. The reaction mixture was filtered through M frit and the filtrate was vacuum dried to give 1-ethyl, 2-methylimidazolium acetate.

1,3-di- ^t -butylimidazolinium acetate, TCS 2 of the present invention
A 1.0 M solution of 1,3-di- ^t -butylimidazolinium BF ₄ was prepared in anhydrous MeOH. To this was added 1.05 equivalents of KOAc as a solid. The mixture was allowed to stir overnight. The reaction mixture was filtered through M frit and the filtrate was dried in vacuo to give 1,3-di- ^t -butylimidazolinium acetate.

1,3-diadamantyl imidazolium acetate, TCS 3 of the present invention
A 1.0 M solution of 1,3-diadamantylimidazolium BF ₄ was prepared in anhydrous MeOH. To this was added 1.05 equivalents of KOAc as a solid. The mixture was allowed to stir overnight. The reaction mixture was filtered through M frit and the filtrate was dried in vacuo to give 1,3-diadamantylimidazolium acetate.

1,3-diisopropylimidazolium acetate, TCS 4 of the present invention
A 1.0 M solution of 1,3-diisopropylimidazolium Cl was prepared in anhydrous MeOH. To this was added 1.05 equivalents of KOAc as a solid. The mixture was allowed to stir overnight. The reaction mixture was filtered through an M frit and the filtrate was vacuum dried to give 1,3-diisopropylimidazolium acetate.

Di- ^t- butyl-imidazolium acetate, TCS 5 of the present invention
Paraformaldehyde (10.0 g, 333 mmol) and 300 ml of toluene were added to a 1 L flask. ^T BuNH ₂ (24.35 g, 333 mmol) was added dropwise at ambient temperature through the addition funnel. After the addition, the solution was heated until homogeneity was just achieved. The resulting solution was cooled in an ice ^bath, it was added further dropwise _{t BuNH 2 (24.35g, 333mmol)} . Acetic acid (20.0 g, 333 mmol) was added through an addition funnel while keeping the reaction in an ice bath. After the reaction was warmed to ambient temperature, 48.3 g of glyoxal (40 wt% in water, 333 mmol) was added dropwise. Two phases were present. The reaction was heated to 40 ° C. overnight. After cooling to about 25 ° C., the layers were separated and the aqueous layer was washed twice with 25 ml ether. By evaporating liquefy the aqueous layer, di - give imidazolium acetate 68.0g of (85.0%) as a brown solid - ^t-butyl.

1-butyl-3-methylimidazolium acetate, TCS 6 of the present invention
A 1.0 M solution of 1-butyl-3-methylimidazolium Cl was prepared in anhydrous MeOH. To this was added 1.05 equivalents of KOAc as a solid. The mixture was allowed to stir overnight. The reaction mixture was filtered through M frit and the filtrate was vacuum dried to give 1-butyl-3-methylimidazolium acetate.

Determination of Catalyst Activation Temperature Each of the inventive trimerized catalyst system (TCS) 1-6 samples was dissolved in diethylene glycol, mixed in PMDI for 45 seconds at about 25 ° C. and placed in a DSC sample pan. The catalyst activation temperature of each invention sample is measured by DSC method as follows. The formation of the trimer is confirmed by IR. The results are shown in Table 1.

(Comparative Example 1)
Comparative samples 1 to 3 are prepared by the same method as samples 1 to 6 of the present invention described above. The catalyst activation temperature of each comparative sample is measured by the DSC method as follows. The formation of the trimer is confirmed by IR. The results are shown in Table 1.

Foam Formation The foam of the present invention is produced on a Cannon HP-60 and Hi Tech Eco-RIM high pressure machine. The overall machine throughput was about 200-225 g / sec. Foam samples were made using a mold preheated to 51.7 ° C. On the other hand, the chemical temperature varied between 21-27 ° C. for the following formulations: polyol (aromatic polyester polyol, 100 php), trimerization catalyst system (less than 6 php), flame retardant (TCPP, 4.7 php), surface activity Agent (1.7 php), urethane catalyst (Polycat ™ 5 catalyst, 0.15 php), blowing agent (n-pentane, 17 php), and a premix of water. Sufficient isocyanate (MDI polymer) and premix are combined to achieve the desired isocyanate index (eg, 270 or 500). The trimer content of the foam 1 of the present invention was measured by ATR-FTIR spectroscopy, and the results are shown in FIG.

(Comparative Example 2)
Comparative foams are produced on a Cannon HP-60 and Hi Tech Eco-RIM high pressure machine. The overall machine throughput was about 200-225 g / sec. Foam samples were made using a mold preheated to 51.7 ° C. On the other hand, the chemical temperature varied between 21-27 ° C. for the following formulations: polyol (aromatic polyester polyol, 100 php), DABCO TMR-2 catalyst (less than 6 php), flame retardant (TCPP, 4.7 php), Surfactant (1.7 php), urethane catalyst (Polycat ™ 5 catalyst, 0.15 php), blowing agent (n-pentane, 17 php), and water premix. Sufficient isocyanate (MDI polymer) and premix are combined to achieve the desired isocyanate index (eg, 270 or 500). The trimer content of comparative foam 1 was measured by ATR-FTIR spectroscopy and the results are shown in FIG.

Test methods The test methods include the following.

Differential Scanning Calorimetry The Differential Scanning Calorimetry (DSC) method is performed using a TA 2920 dual sample DSC. Samples are processed in an aluminum DSC pan that is hermetically sealed with a hole in the lid for venting. The catalyst charge is about 1 mol% based on the total isocyanate in 1 g of PAPI 20 MDI polymer. For standard processing, no additional —OH is added to the formulation other than that present in the catalyst solution. Samples are prepared and analyzed by the following method.
1. Add catalyst solution to 20 ml vial and record mass.
2. About 1.0 g of PAPI 20 is added to the vial and the mixture is stirred with a Teflon® coated spatula for about 45 seconds.
3. Remove two aliquots (1-10 mg) and place in the pre-weighed DSC pan bottom, then seal the pan hermetically.
4). The sample is then immediately placed in a TA 2920 DSC with a similar pan as a reference.
5. A single scan is performed to 190 ° C at a rate of 10 ° C / min.
6). Calculate the exothermic onset temperature and peak maximum temperature and the total heat of the exothermic peak. The peak maximum temperature can generally be used for catalyst comparison / evaluation. This is because the calculated starting temperature can vary by as much as 3 ° C. depending on the point selection in a single spectrum.
7). The apparatus is then air cooled to below 35 ° C. before processing the next sample.

  Sample replicas are processed to obtain a total of 4 spectra (2 replicates for each of the 2 replica samples). Depending on the amount of —OH in the catalyst solution, the isocyanate index of the “formulation” can range from 1000 to 3500. In the index 1000 formulation, 90% of the initial isocyanate can be used exclusively for the trimerization reaction and the remaining 10% is used for the reaction with the hydroxyl groups of the catalyst solvent. At these levels, the main exotherm is believed to be the exotherm of the trimerization reaction.

Fourier transform infrared (FTIR) for trimer content
At the center of each rigid foam panel, collect a 1 inch x 1 inch x 3 inch sample over the panel thickness. Each sample is then cut along a thickness of 3 inches to form a 5 mm thick section. However, the outermost end (that is, the outer surface) is cut to a thickness of 2 to 3 mm. ATR-FTIR measurements are performed on a Nicolet Magna FTIR instrument fitted with a Durascope 1 Bounce ATR diamond crystal accessory. Typically, 16 scans are acquired in the spectral range of 4000-600 cm ⁻¹ . The resolution is 4 cm ⁻¹ , the velocity is 0.6329, and the aperture is 138. FTIR spectra are acquired at 6 different locations at each depth (3 locations on each opposing section at a given depth). However, the measurement is performed at four positions on the outer surface.

Trimer Content A typical attenuated total reflection Fourier transform infrared (ATR-FTIR) spectrum of a rigid PIR foam is shown below. The peak at 1410 cm ⁻¹ is specific for the trimer 6-membered ring, while the various carbonyl vibrational modes found in the urethane, urea, trimer, and ester moieties are all around 1700 cm ⁻¹ as a single peak. Appears in The small peak at 2275 cm ⁻¹ corresponds to free unreacted isocyanate groups, while the aromatic peak at 1595 cm ⁻¹ is generally used as an internal standard to normalize the data.

Aromatic peak height (about 1595cm ^-1) in normalized NCO peak height (about 2275 cm ^-1) typically indicates the amount of unreacted isocyanate groups in the foam, whereas We aromatic peak height The normalized trimer peak height (about 1410 cm ⁻¹ ) typically indicates the amount of isocyanurate trimer species in the foam panel. To determine the trimer content profile across the depth of each panel, samples are collected, sectioned, and FTIR spectra acquired by the method described above. Average the peak ratio at a given depth. The standard deviation represents the spread of the peak ratio value across various locations at a given depth in the sample. These amounts indicate the distribution of unreacted isocyanate groups and isocyanurate trimers (ie depth profile) over the panel depth.

  The present invention may be embodied in other forms without departing from the spirit and essential characteristics thereof, and thus the scope of the invention is indicated by the appended claims rather than by the foregoing specification. Reference should be made to the scope of

Claims (15)

A trimerization catalyst system comprising an imidazolium or imidazolinium cation; and an isocyanate trimer derived anion and having a trimerization activation temperature in the range of 73 ° C. or less. At least 25% by weight of polyol, based on the weight of the precursor formulation;
An imidazolium or imidazolinium cation; and an isocyanate trimer derived anion having a trimerization activation temperature in the range of 73 ° C. or less, and a trimerization catalyst system of 15 wt% or less relative to the weight of the precursor formulation. And optionally one or more surfactants, one or more flame retardants, water, one or more antioxidants, one or more foaming aids, one or more urethane catalysts A precursor formulation comprising one or more trimerization cocatalysts, or combinations thereof. Providing one or more monomers selected from the group consisting of isocyanates, diisocyanates, triisocyanates, isocyanate oligomers, salts of any of them, and mixtures of any of them;
Providing a trimerization catalyst system comprising an imidazolium or imidazolinium cation and an isocyanate trimer derived anion and having a trimerization activation temperature in the range of 73 ° C. or less;
Trimerizing the one or more monomers in the presence of the trimerization catalyst;
A process for the trimerization of isocyanate comprising the step of thereby producing one or more isocyanurate trimers. Providing one or more monomers selected from the group consisting of isocyanates, diisocyanates, triisocyanates, isocyanate oligomers, salts of any of them, and mixtures of any of them;
Providing a polyol;
Providing a trimerization catalyst system comprising an imidazolium or imidazolinium cation and an isocyanate trimer derived anion and having a trimerization activation temperature in the range of 73 ° C. or less;
Optionally, one or more surfactants, one or more flame retardants, water, one or more antioxidants, one or more foaming aids, one or more urethane catalysts, Providing one or more trimerization cocatalysts, or combinations thereof;
Contacting the one or more monomers and the polyol, optionally with the one or more surfactants, and optionally with the one or more flame retardants, and optionally The water, and optionally the one or more antioxidants, and optionally the one or more blowing aids in the presence of the trimerization catalyst system, and optionally the Contacting one or more urethane catalysts and optionally the one or more trimerization cocatalysts;
A method for producing a polyisocyanurate / polyurethane rigid foam comprising the step of thereby producing said polyisocyanurate / polyurethane rigid foam.   A trimerization catalyst system comprising an imidazolium or imidazolinium cation and an isocyanate trimer derived anion, optionally with one or more surfactants, optionally with one or more flame retardants, Water as needed, optionally one or more antioxidants, optionally one or more foaming aids, optionally one or more additional urethane catalysts, and optionally 1 Isocyanates, diisocyanates, triisocyanates, isocyanates in the presence of a trimerization catalyst system comprising one or more trimerization cocatalysts, or optionally combinations thereof, and having a trimerization activation temperature in the range of 73 ° C. or less One or more selected from the group consisting of oligomers, salts of any of them, and mixtures of any of them Comprising the reaction product of a monomer and a polyol, polyisocyanurate / polyurethane rigid foams. A trimerization catalyst system comprising an imidazolium or imidazolinium cation and an isocyanate trimer derived anion, optionally with one or more surfactants, optionally with one or more flame retardants, Water as needed, optionally one or more antioxidants, optionally one or more foaming aids, optionally one or more additional polyurethane catalysts, and optionally Isocyanates, diisocyanates, triisocyanates, isocyanate oligomers, salts of any of them, and any of their salts in the presence of a trimerization catalyst system that includes one or more trimerization catalysts, or optionally combinations thereof Including the reaction product of one or more monomers selected from the group consisting of Polyisocyanurate trimerization ratio as measured by ATR-FTIR spectroscopy at a depth of 12mm from the upper surface of the rigid foam _(Abs 1410 _/ Abs ₁₅₉₅₎ is at least 5, polyisocyanurate / polyurethane rigid foams. The imidazolium or imidazolinium cation has the following structure:
Wherein E is a C ₂ or C ₆ unsaturated bond, X is selected from the group consisting of H, C ₁ -C ₁₈ , P, Si, N, and any combination thereof, R ₁ is H, C ₁ -C ₁₈ , Si and any combination thereof are selected, and R ₂ is selected from the group consisting of H, C ₁ -C ₁₈ , Si and any combination thereof)
The trimerization catalyst system according to any one of claims 1 to 6, comprising:   The trimerization catalyst system according to any of claims 1 to 6, wherein the imidazolium or imidazolinium cation is tetraethylimidazolium or imidazolinium cation or tetrabutylimidazolium or imidazolinium cation.   7. The isocyanate trimer derived anion is selected from the group consisting of carboxylate, carbonate, phenoxide, amide, amidinate, imide, phosphide, thiocyanate, thioisocyanate, isocyanate, cyanate, and fluoride. A trimerization catalyst system according to claim 1.   The trimerization catalyst system according to any of claims 1 to 6, wherein the isocyanate trimer derived anion is selected from the group consisting of carboxylate, carbonate, phenoxide, and fluoride. The isocyanate trimer derived anion has the following structure:
Wherein X ′ is selected from the group consisting of H, C ₁ -C ₁₈ , aliphatic, aromatic, cyclic, acyclic, acyl and their derivatives.
The trimerization catalyst system according to claim 1, which is a carboxylate having   The trimerization catalyst system of claim 11, wherein the carboxylate is selected from the group consisting of formate, acetate, octanoate, 2-ethylhexanoate, benzoate, and substituted derivatives thereof.   13. A trimerization catalyst system according to claim 12, wherein the isocyanate trimer derived anion is acetate.   The trimerization catalyst system according to any of claims 1 to 6, which is tetrabutylimidazolium acetate or tetrabutylimidazolinium acetate, or tetraphenylimidazolium acetate or tetraphenylimidazolinium acetate.   The rigid polyisocyanurate foam according to any one of claims 4 to 6, wherein the foam is used as a heat insulating material.